9th International Rubber Glove Conference & Exhibition 2018

THEORETICAL EXPLANATIONS ON SOME UNIQUE PROPERTIES

OF NITRILE LATEX AND FILM

ENG Aik Hwee*

Malaysian Rubber Export Promotion Council (MREPC)
Kuala Lumpur, Malaysia

*engah@mrepc.com; engaikhwee@gmail.com
Eng Aik Hwee obtained his Doctorate in Functional Materials
Engineering from Tokyo University of Agriculture &
Technology in 1994. He has more than 30 years of
experience in the latex and rubber research. Currently, he is
an independent technical advisor and trainer of MREPC. He is
also a member of the Industrial Advisory Panel for the
Polymer Engineering & Materials Engineering Programmes,
Perlis University of Malaysia.

“Disclaimer: The information in this paper has been compiled by the author for
educational purpose and does not necessarily represent the views or opinions of
MREPC. It may contain intellectual property rights owned by the respective
company or individual. The readers are advised to exercise due diligence before
use. ”

ABSTRACT

Due to the increasing demand for synthetic examination gloves, the use of nitrile
latex to manufacture examination glove is getting more popular these days. Like
natural rubber (NR) latex, nitrile latex can be used to produce high quality
examination gloves meeting the requirements of different international standards.
Despite these, there are several unique properties of nitrile latex and film, which are
not found in those of natural rubber latex. These include better ozone resistance and
thermal aging resistance, thinner film than those of NR gloves. On the other hand,
nitrile latex is also known to have higher surfactant and poorer wet gel strength than
NR latex. Unlike NR latex, which can be fully prevulcanised in latex state, a fully
prevulcanised nitrile latex appears to be more difficult to achieve. This paper intends
to explain these unique properties based on the theoretical understanding of the
latex and film systems.

BACKGROUND

NR latex has been used as a material for the commercial production of NR gloves for
a long time and the demand for such products remains high until today. However,
due to the NR protein allergy issue, the market share and growth rate of synthetic

Page 1 of 5
9th International Rubber Glove Conference & Exhibition 2018

rubber gloves are also significantly high in recent years. Currently, the most widely
used synthetic rubber gloves are nitrile examination gloves. The technology for
producing nitrile examination gloves is very similar to that of NR gloves. The gloves
are able to meet the requirements of major international standards for examination
gloves such as EN455 series, ASTM D6719 and ISO 11193. Despite these, there are
several unique properties of nitrile examination gloves, which are not found in the
NR gloves. This paper intends to offer some possible explanations for these
properties. A better understanding on the latex and film properties is expected to
help in the new product design, production process as well as trouble-shooting.

THICKNESS

It is a well-known fact that nitrile examination gloves can be made much thinner
than NR examination gloves. Generally, when a thinner latex film is made, the defect
rate is expected to increase significantly. This is because impact of the surface
imperfection on quality of a thin film is much higher than that on a thick film. The
ability of nitrile latex to form thinner film than NR latex is most likely due to two
reasons. Firstly, the particle size of nitrile latex [1] is about 8-10 times smaller than
that of NR latex concentrate [2]. A smaller particle size means that the number of
particle layers stacking up is also 8-10 times higher than that of NR latex to form the
same thickness. Therefore, any imperfection on the nitrile film surface, such as
absence of a few layers of particle, is expected to have less impact on cracks
formation and the physical properties such as tensile strength, compared to that on
the NR film surface.
Due to its narrower particle size distribution which leads to more “void volume” than
NR latex, and also the lower dry rubber content used, these lead to nitrile latex film
to have a higher shrinkage rate than that of NR latex film. This does not favour the
formation of thin film because it will result in high stress and lead to cracks
formation particularly at the finger crotch areas. However, nitrile rubber is able to
reduce the stress that is generated by the shrinkage via the stress relaxation, a
property that is not found in NR, reducing the tendency of the film to crack during
the drying process.

OZONE CRACKING

Ozone attack on rubber may lead to ozone cracking problem. This problem is
normally found in NR gloves but rarely in nitrile gloves, despite that nitrile rubber
also contains the unsaturated carbon-carbon double bonds, i.e. the butadiene
repeating units. At the initial stage of ozone attack on the NR double bonds, it occurs
very rapidly on the exposed surface. If there is stress applied to the NR surface
during the reaction, degradation at the areas of high strain creates a retractive force
causing the underlying rubber chains to become exposed to the surface and
therefore ozone on the exposed rubber continues [3]. This eventually leads to the
formation of ozone cracks. In the case of NR gloves, the folded edge is an area where
it is under stress when the gloves are stacked up and packed in a non-airtight
dispenser box. Therefore, ozone cracking normally occurs at the folded edge during
storage. Due to stress relaxation properties of nitrile glove, the folded edge of nitrile

Page 2 of 5
9th International Rubber Glove Conference & Exhibition 2018

gloves, on the other hand, is significantly not strained. This could explain the lower
tendency of nitrile gloves to have ozone cracking issue.

AGEING PROFILE

The tensile properties such as force at break and ultimate tensile strength of NR
gloves normally decrease with accelerated ageing time or real time ageing during the
shelf life study. In the case of nitrile gloves, however, the tensile properties increase
at the initial stage of ageing, and then decrease on prolonged ageing [4]. In the
previous ageing studies on nitrile rubbers and gloves, it was found the carbonyl
formation was initially fast and quickly became stagnant after some time, indicating
low level or unavailability of oxygen [5]. This is because the acrylonitrile group
imparts the low gas permeability property to the nitrile rubber. Therefore, a high
unsaturation level of nitrile rubber has been found to favour the formation of
crosslinking types of reactions during ageing due to the formation of more radicals
and subsequently recombination of the radicals to form crosslinks. On the other
hand, the gas permeability of NR gloves is known to be high, as indicated by the
inability of an inflated balloon to retain the gas over a day. During the ageing, the
relatively fast permeation of oxygen facilitates the degradation reactions.

PUNCTURE RESISTANCE

The puncture resistance of rubber gloves depends on the test method used. The
ASTM F1342 and EN388 methods use a probe with a rounded tip while ASTM F2878
uses a hypodermic needle with a sharp tip [6,7]. Nitrile gloves are known to have a
better puncture resistance than NR gloves when a rounded probe is used. This is
because when a blunt probe is used, the puncture is controlled by a local
deformation or failure strain. Therefore, when puncture occurs instantly at
maximum load where the strain at the probe tip reaches the failure value. It is well
known that the force required to puncture rubber increases with increasing
thickness. Because nitrile gloves are stiffer and less stretchable than NR gloves, the
thickness at the highest strained area is higher, allowing a higher load before the
failure strain is achieved. However, when tested against sharp objects such as
hypodermic needles, the puncture resistance of nitrile gloves is comparable to that
of NR gloves. This is because the needles penetrate gradually through the sample
thickness; after the force reaches a maximum, it diminishes slightly before reaching a
plateau. The “thickness effect” that is due to the rubber deformation is not an
important factor in determining the puncture force but it is the needle penetration
through the rubber layer that leads to the puncture.

PREVULCANISATION

Prevulcanisation is a crosslinking reaction of rubber molecules in latex state. Because

the rubber molecules in latex are confined in the particles, the crosslinking reactions
among the rubber molecules can only occur within the same latex particles. Upon
completion of the reactions, the unreacted vulcanizing agents are normally removed
by clarification or centrifugation. Because of low level of unreacted vulcanizing

Page 3 of 5
9th International Rubber Glove Conference & Exhibition 2018

agents, the prevulcanised latex remains stable, over a longer period of time, i.e. in
terms of the shelf life and pot-life. Since the rubber molecules in prevulcanised latex
are optimally vulcanized in latex state for product applications, no further
vulcanization is required during the processing of latex to form products. Unlike post
vulcanization system where the oven temperature fluctuation could impact the
crosslink density and consequently the physical properties of the rubber product,
this is not the case for prevulcanised latex. So far, only NR latex can be fully
prevulcanised in latex state. Attempt to commercially produce prevulcanised
synthetic latexes has so far been unsuccessful. One of the reasons for this is due to
the high surfactant level in these latexes which could inhibit inter-particle integration
after prevulcanisation. In the case of nitrile latex, the problem is compounded by the
relatively high glass transition temperature of nitrile rubber (-27 oC) compared to NR
(-70oC) which further reduces the segmental mobility of the rubber molecules upon
prevulcanisation. This is expected to further hinder the inter-particles integration,
leading to the film cracking issue after the rubber is fully prevulcanised. Inter-
particles integration or film formation could be improved via several approaches;
namely 1) increasing the drying temperature; 2) reducing the surfactant content; 3)
reducing the glass transition temperature by incorporating suitable plasticisers,
which could be achieved via the following (a) increasing hydrophilic properties of the
rubber to allow the retained water to act as a plasticiser; (b) using surfactant that is
compatible with the rubber to plasticise the rubber. Increasing the drying
temperature may lead to a higher film shrinkage which leads to the cracking issue.
Plasticising the nitrile rubber appears to be a viable solution for the prevulcanisation
of nitrile latex.

REFERENCES

1. Llosen, MA, Gugliotta, LM, Meira, GR, Particle Size Distribution of SBR and NBR
Latexes by UV-VIS Turbidimetry Near the Rayleigh Region. Rubb. Chem. Technol.,
69, 696-712 (1996)
2. Sakdapipanich, JT, Rojruthai, P, Molecular Structure of Natural Rubber and Its
Characteristics Based on Recent Evidence. In Reda Sammour (Eds.), Biotechnology
- Molecular Studies and Novel Applications for Improved Quality of Human Life,
Published by Intechopen. Chapter 13 (2012)
http://cdn.intechopen.com/pdfs/29737/InTech-
Molecular_structure_of_natural_rubber_and_its_characteristics_based_on_rece
nt_evidence.pdf
3. Gilbert JH, Degradation and Cracking of Elastomers by Ozone. Proc. 4th Rubb
Technol. Conf. London. Messenger, T.H., ed, 696-710, (1962)
4. Foo YT, A Study of the Thermal Ageing of Carboxylated Nitrile Rubber Latex Thin
Films. M.Sc. Dissertation. Universiti Tunku Abdul Rahman (2013)
http://eprints.utar.edu.my/1866/1/
A_Study_of_Thermal_Ageing_of_Carboxylated_Nitrile_Rubber_Latex_Thin_Films
.pdf
5. Pazur RJ, Cormier JG, Korhan-Taymaz K, The Effect of Acrylonitrile Content on the
Thermooxidative Aging of Nitrile Rubber. Rubb. Chem. Technol., 87, 53–69 (2014)

Page 4 of 5
9th International Rubber Glove Conference & Exhibition 2018

6. Patel HB, Fleming G.JP, and Burke FJT, Puncture resistance and stiffness of nitrile
and latex dental examination gloves. Br. Dent. J., 196, 695-700 (2004).
7. Nguyen CT, Vu-Khanh, T , Dolez PI. · Lara J, Puncture of elastomer membranes by
medical needles. Part I: Mechanisms. Int. J. Fract., 155, 75–81 (2009)

Page 5 of 5